US20150158976A1 - Alkanolysis process and method for separating catalyst from product mixture - Google Patents

Alkanolysis process and method for separating catalyst from product mixture Download PDF

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Publication number
US20150158976A1
US20150158976A1 US14/407,296 US201314407296A US2015158976A1 US 20150158976 A1 US20150158976 A1 US 20150158976A1 US 201314407296 A US201314407296 A US 201314407296A US 2015158976 A1 US2015158976 A1 US 2015158976A1
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United States
Prior art keywords
exchange resin
reactor
catalyst
alkanol
polyether polyol
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Abandoned
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US14/407,296
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English (en)
Inventor
Suri N. Dorai
Qun Sun
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Invista North America LLC
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Invista North America LLC
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Publication date
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Priority to US14/407,296 priority Critical patent/US20150158976A1/en
Assigned to INVISTA NORTH AMERICA S.A.R.L. reassignment INVISTA NORTH AMERICA S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUN, QUN, DORAI, SUN N.
Publication of US20150158976A1 publication Critical patent/US20150158976A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside

Definitions

  • the present invention relates to an improved process and apparatus for alkanolysis of polyether polyol esters to polyether polyols. More particularly, the invention relates to the alkanolysis of polytetramethylene ether diacetate to polytetraalkylene ether glycol in the presence of a C 1 to C 4 alkanol and an alkali or alkaline earth metal catalyst wherein the catalyst component of the product mixture comprising polytetraalkylene ether glycol, alkanol and catalyst, essentially free of the alkanol acetate by-product, e.g., methyl acetate is removed by contacting the mixture in the absence of added water with certain ion exchange resin at specified contact conditions.
  • step (3) contacting the recovered reaction zone effluent of step (2), in the absence of added water, with a strongly acidic ion exchange resin with active sites less than or equal to 5.3 eq/kg, surface area of from about 30 to about 70 m2/gram in the form of particles of any suitable size consistent with ease of handling and pressure drop across the reactor bed, for example, particle sizes greater than 0.5 mm, said contacting being performed at conditions including temperature of from liters feed/liters of resin-hour 40 to 80° C., for example 40 to 70° C., pressure from ambient to 3 bars, and/or flow rate from 0.5 to 5.0 liters feed/liters of resin-hour and (4) recovering effluent from contacting step (3) comprising less than 1.0
  • An embodiment of the present invention comprises a method for removing alkali or alkaline earth metal catalyst from a mixture comprising polytetraalkylene ether glycol, alkanol and alkali or alkaline earth metal catalyst, which comprises steps of: (1) contacting the mixture with ion exchange resin with active sites less than or equal to 5.3 eq/kg, surface area of from about 30 to about 70 m2/gram in the form of particles of any suitable size consistent with ease of handling and pressure drop across the reactor bed, for example, particle sizes greater than 0.5 mm, at contact conditions including a temperature of from 40 to 80° C., for example 40 to 70° C., pressure from ambient to 3 bars, and/or flow rate from 0.5 to 5.0 liters feed/liters of resin-hour, and (2) recovering effluent mixture from step (1) comprising less than 1.0 ppm alkali or alkaline earth metal ions.
  • Another embodiment of the present invention comprises an apparatus for converting the diester of a polyether polyol to a corresponding dihydroxy polyether polyol, comprising: (1) a reactor for contacting the diester of a polyether polyol and a C 1 to C 4 alkanol with alkali or alkaline earth metal catalyst to convert at least a portion of the diester, for example >99 wt. %, for example >99.99 wt.
  • the polyether polyol diester composition used herein is generally any polyether such as polyether typically produced via an acid catalyzed ring opening polymerization reaction of a cyclic ether or mixture in the presence of a carboxylic acid and carboxylic acid anhydride wherein tetrahydrofuran is the major and/or dominant reactant; i.e., substantial THF being incorporated into the PTMEA product.
  • the alkanolysis step of the present invention is generally carried out at from about 60° C. to about 90° C.
  • the pressure is ordinarily atmospheric pressure, but reduced or elevated pressure may be used to aid in controlling the temperature of the reaction mixture during the reaction.
  • the pressure employed may be from about 1 to about 50 psig.
  • the effluent 5 comprising less than 1.0 ppm alkali or alkaline earth metal ions is recovered from the exchange resin column 20 .
  • the apparatus of the invention may comprises 2 exchange resin columns, wherein one performs the contacting, while the other is regenerated or stands by.
  • the valves 40 is opened or closed to direct the effluent 4 into one or both of the exchange resin column.
  • the number average molecular weight of the PTMEG product of this invention can be as high as about 30,000 dalton, for example, 10,000 dalton, but will usually range from 500 to about 5000 dalton, and more commonly will range from about 500 to 3000 dalton.
  • the product mixture of the alkanolysis process will commonly comprise from about 50 to about 80 wt. % polytetraalkylene ether glycol, e.g. PTMEG, from about 20 to about 50 wt. % alkanol, e.g. methanol, and from 100 to 2000 ppm catalyst.
  • the present process can be carried out in any suitable reactor, such as a continuous stirred tank reactor (CSTR), a batch reactor, a tubular concurrent reactor or any combination of one or more reactor configurations known to those skilled in this art.
  • CSTR continuous stirred tank reactor
  • a batch reactor a batch reactor
  • a tubular concurrent reactor any combination of one or more reactor configurations known to those skilled in this art.
  • reactive distillation a single distillation column can be employed in a continuous manner.
  • the reactive distillation can be performed by any of the distillation process and equipment as generally known and practiced in the art.
  • a deep seal sieve tray distillation column can be used.
  • a conventional tray distillation column is similarly suitable.
  • the PTMEG was obtained from INVISTA.
  • Anhydrous methanol and anhydrous sodium methoxide (NaOCH 3 )/methanol solutions were obtained from Sigma-Aldrich Chemicals.
  • Amberlyst-15 sulfonic acid resin a strong acid ion exchange resin was obtained from Dow Chemical Company.
  • Amberlyst-15 is used, but any suitable acid resin with comparable properties is acceptable.
  • a suitable ion exchange resin can have active sites less than or equal to 5.3 eq/kg, surface area of from about 30 to about 70 m2/gram, and be in the form of particles of any suitable size consistent with ease of handling and pressure drop across the reactor bed, for example, particle sizes greater than 0.5 mm.
  • the Amberlyst-15 resin Prior to use, an optional step was carried out to remove any color and free acid, the Amberlyst-15 resin was rinsed with an acetone/deionized water mixture multiple times, for example, 4 times, followed by further rinses with deionized water multiple times, for example, 6 times, until the rinse water was nearly neutral, for example, the pH was in the range of 5 to 7.
  • the Amberlyst-15 resin was then dried in a full vacuum oven at 95° C. overnight to remove residue moisture before packing the resin into a fixed bed glass column for the experiments.
  • the presence of methanolysis catalyst in mixtures was determined by acid-base titration carried out using a Metrohm Autotitrator with a method similar to ASTM D4662-93.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polyethers (AREA)
US14/407,296 2012-06-22 2013-06-12 Alkanolysis process and method for separating catalyst from product mixture Abandoned US20150158976A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/407,296 US20150158976A1 (en) 2012-06-22 2013-06-12 Alkanolysis process and method for separating catalyst from product mixture

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201261663015P 2012-06-22 2012-06-22
US14/407,296 US20150158976A1 (en) 2012-06-22 2013-06-12 Alkanolysis process and method for separating catalyst from product mixture
PCT/US2013/045412 WO2013191987A1 (en) 2012-06-22 2013-06-12 Improved alkanolysis process and method for separating catalyst from product mixture and apparatus therefor

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US (1) US20150158976A1 (enrdf_load_stackoverflow)
EP (1) EP2864392A4 (enrdf_load_stackoverflow)
KR (1) KR20150024840A (enrdf_load_stackoverflow)
CN (2) CN103509177B (enrdf_load_stackoverflow)
BR (1) BR112014029525A2 (enrdf_load_stackoverflow)
IN (1) IN2015MN00017A (enrdf_load_stackoverflow)
RU (1) RU2014149845A (enrdf_load_stackoverflow)
WO (1) WO2013191987A1 (enrdf_load_stackoverflow)

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Publication number Priority date Publication date Assignee Title
CN105131274B (zh) * 2015-08-20 2017-11-10 西安蓝晓科技新材料股份有限公司 一种用于聚四氢呋喃生产中除钠离子的方法
EP3392288A1 (en) 2017-04-21 2018-10-24 Sulzer Chemtech AG A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001011173A (ja) * 1999-06-30 2001-01-16 Mitsubishi Chemicals Corp ポリテトラメチレンエーテルグリコールの製造方法

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US4584414A (en) * 1984-12-21 1986-04-22 E. I. Du Pont De Nemours And Company Process for preparing improved poly(tetramethylene ether) glycol by alcoholysis
US4985551A (en) * 1988-12-29 1991-01-15 Basf Corporation Process for purification of catalysts from polyols using ion exchange resins
US5254227A (en) 1989-06-16 1993-10-19 Olin Corporation Process for removing catalyst impurities from polyols
AU5847590A (en) * 1989-06-16 1991-01-08 Olin Corporation Process for removing ionizable impurities from non-aqueous fluids
US5852218A (en) * 1995-12-14 1998-12-22 E. I. Du Pont De Nemours And Company Alkanolysis of polyether polyol esters by reactive distillation
DE19758296A1 (de) 1997-12-31 1999-07-01 Basf Ag Herstellung von Polytetrahydrofuran mit endständigen Hydroxylgruppen unter Verwendung von Ionenaustauschern
JPH11279275A (ja) * 1998-03-27 1999-10-12 Mitsubishi Chemical Corp ポリテトラメチレンエーテルグリコールの製造方法
JP3837966B2 (ja) * 1999-06-22 2006-10-25 三菱化学株式会社 ポリテトラメチレンエーテルグリコールの製造方法
DE10032266A1 (de) 2000-07-03 2002-01-17 Basf Ag Verbessertes Verfahren zur einstufigen Herstellung von Polytetrahydrofuran und Tetrahydrofuran-Copolymeren
DE10112116A1 (de) * 2001-03-14 2002-09-19 Basf Ag Verfahren zur Herstellung von Polyetherolen mit definiertem CPR-Wert
DE10140949A1 (de) 2001-08-21 2003-03-06 Basf Ag Verfahren zur Herstellung einer alkoholischen Lösung von Polytetrahydrofuran mit endständigen OH-Gruppen
CN101080433B (zh) * 2005-03-17 2012-06-27 三菱化学株式会社 聚醚多元醇化合物的制造方法
KR20130127550A (ko) * 2008-05-15 2013-11-22 아사히 가세이 케미칼즈 가부시키가이샤 이소시아네이트의 제조 방법
US20140378712A1 (en) * 2012-01-26 2014-12-25 Invista North America S.A.R.L. Alkanolysis process

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Publication number Priority date Publication date Assignee Title
JP2001011173A (ja) * 1999-06-30 2001-01-16 Mitsubishi Chemicals Corp ポリテトラメチレンエーテルグリコールの製造方法

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EP2864392A4 (en) 2015-12-23
IN2015MN00017A (enrdf_load_stackoverflow) 2015-10-16
CN204138580U (zh) 2015-02-04
RU2014149845A (ru) 2016-08-10
WO2013191987A1 (en) 2013-12-27
CN103509177B (zh) 2017-04-12
CN103509177A (zh) 2014-01-15
EP2864392A1 (en) 2015-04-29
BR112014029525A2 (pt) 2017-06-27
KR20150024840A (ko) 2015-03-09

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DORAI, SUN N.;SUN, QUN;SIGNING DATES FROM 20141226 TO 20150109;REEL/FRAME:034674/0173

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